Chapter 5

THE SECOND LAW OF

THERMODYNAMICS

By: Dr. Muhammad Ayoub

 Contents
 Introduce the second law of thermodynamics.
 Identify valid processes as those that satisfy both
the first and second laws of thermodynamics.
 Discuss thermal energy reservoirs, reversible and
irreversible processes, and heat engines.
 Describe the Kelvin–Planck and Clausius
statements of the second law of thermodynamics.
 Describe the Carnot cycle.
 Examine the Carnot principles and idealized
Carnot heat engines,
 Determine the expressions for the thermal
efficiencies for reversible heat engines .
Learning Outcome
By the end of this lecture, you are expected to:
 Explain the second law of thermodynamics and its
application to heat engine
 Discuss thermal energy reservoirs, reversible and
irreversible processes, heat engines,
 Determine the expressions for the thermal efficiencies
and for reversible heat engines

2
 Objectives

• Introduce the second law of thermodynamics.

• Identify valid processes as those that satisfy both the first
and second laws of thermodynamics.
• Discuss thermal energy reservoirs, reversible and
irreversible processes, and heat engines.
• Describe the Kelvin–Planck and Clausius statements of the
second law of thermodynamics.
• Describe the Carnot cycle.
• Examine the Carnot principles and idealized Carnot heat
engines,
• Determine the expressions for the thermal efficiencies for
reversible heat engines .
 Introduction to the Second Law
A cup of hot coffee does
not get hotter in a cooler
room.

Transferring
heat to a
paddle wheel
will not cause
it to rotate.

These processes
cannot occur even
Transferring though they are not in
heat to a wire violation of the first law.
will not
generate
electricity.
Introduction to the Second Law
Statement of the Second Law
Statement 1
No apparatus can operate in such a way that its only effect
(in system & surroundings) is to convert heat absorbed by a
system completely into work by the system.

Statement 2 (Clausius statement)

Heat cannot spontaneously flow from a cold object to a hot
one, whereas the reverse, a spontaneous flow of heat from a
hot object to a cold one, is possible.

Processes occur in a certain direction,

not in just any direction.
The Second Law of Thermodynamics:
Kelvin–Planck Statement
It is impossible for any
device that operates on a
cycle to receive heat from a
single reservoir and produce |QH| = 100 kW
a net amount of work.
|W| = 100 kW
No heat engine can have a thermal
efficiency of 100%. For a power Heat
plant to operate, the working fluid Engine
must exchange heat with the
environment as well as the furnace.
|QC| = 0
The impossibility of having a 100%
efficient heat engine is not due to A heat engine that violates the
friction or other dissipative effects. It Kelvin-Planck statement of the
is a limitation that applies to both the second law.
idealized and the actual heat engines.
The Second Law of Thermodynamics:
Kelvin–Planck Statement
It is impossible for any system to operate in a thermodynamic cycle &
deliver a net amount of work to its surroundings while receiving energy
by heat transfer from a single thermal reservoir.

The statement does not rule out the possibility of a system developing
a net amount of work from a heat transfer drawn from a single
reservoir. It only denies this possibility if the system undergoes a
thermodynamic cycle.

Is this system undergo

thermodynamic
cycle?
THERMAL ENERGY RESERVOIRS

A source
supplies
energy in the
form of heat,
and a sink
absorbs it.
Bodies with relatively large thermal
masses can be modeled as thermal
energy reservoirs.

 Thermal energy reservoir: A hypothetical body that can absorb o reject finite
amounts of heat isothermally (e.g., River, Ocean, Industrial furnace)
 Work reservoir - sufficiently large system in stable equilibrium to which
and from which finite amounts of work can be transferred adiabatically
without any change in its P.
 Thermodynamic cycle - when the system undergoes a series of
processes & then returns to its original state, so that the properties of the
system at the end of the cycle are the same as its beginning.
Introduction to Heat Engines:
Devices or machines that produce work from heat in a cyclic process.

Heat Engines:
Devices that convert heat to work.
1. They receive heat from a heat
reservoir or high-temperature source
|QH| (solar energy, oil furnace, nuclear
reactor, etc.).
2. They convert part of this heat to work
(usually in the form of a rotating
shaft.)
|W| 3. They reject the remaining waste heat
to a cold reservoir or low-
|QC| temperature sink (the atmosphere,
rivers, etc.).
4. They operate on a cycle (returns to its
initial state). Heat engines and other
cyclic devices usually involve a fluid
to and from which heat is transferred
Part of the heat received by a heat
while undergoing a cycle. This fluid is
engine is converted to work, while the
rest is rejected to a cold reservoir (sink) called the working fluid.
Heat Engines: For example, steam power plant
Can we save 𝑸𝒐𝒖𝒕 ?

• In a steam power plant, the condenser is the device where

large quantities of waste heat is rejected to rivers, lakes or
atmosphere.

• Q: Can we take the condenser out of the plant and save all
that waste energy?
The answer is, unfortunately, a firm no for the simple
reason that without a heat rejection process in a
condenser, the heat-engine cycle cannot be completed.

A heat-engine cycle cannot be completed without rejecting

some heat to the cold reservoir. In order words, every heat
engine must waste some energy by transferring it to a low-
temperature reservoir in order to complete the cycle, even
under idealized conditions.
Heat Engines: Net work output and thermal energy
• Energy cycles include the heat engine cycles and refrigeration
cycles.
• In all energy cycles, there are hot and cold reservoirs which are
maintained at constant temperatures, 𝑇𝐻 and 𝑇𝐶 respectively.
• In a heat engine, the working fluid absorbs heat |𝑄𝐻 | from a heat
reservoir, produces a net amount of work |𝑊|, discards heat |𝑄𝐶 | to
a cold reservoir, and returns to its initial state.
• The first law reduces to
𝑊 = 𝑄𝐻 − 𝑄𝐶 − (5.1)
• Thermal efficiency of the engine is defined as the net work output
over heat absorbed or amount of useful work over total energy.
|𝑊| 𝑄𝐻 − |𝑄𝐶 | 𝑄𝐶
𝜂= = = 1− − (5.2)
|𝑄𝐻 | |𝑄𝐻 | 𝑄𝐻
• No engine has ever been built with 100% thermal efficiency, where
|𝑄𝐶 | is zero.
Heat Engines: Thermal energy

QC

TC

Some heat engines perform better

than others (convert more of the
heat they receive to work).

QC
Class example: 1
A steam power plant produces 50 MW of net work while burning fuel to
produce 150MW of heat energy at the high temperature. Determine the
cycle thermal efficiency and the heat rejected by the cycle to the
surroundings.

Solution: Wnet,out
th 
QH
50MW
  0.333  33.3%
150MW
Wnet,out = QH - QC

QC = QH - Wnet,out

= 150 MW - 50 MW

= 100 MW
Class example: 2 (Example 5-17, Cengel)
A 600-MW steam power plant, which is cooled by a nearby river, has a
thermal efficiency of 40%. Determine the rate of heat transfer to the river
water. Will the actual heat transfer rate be higher or lower than this value?
State why?
Solution:
Assumptions: (1) The plant operates steadily (2) The heat losses
from the working fluid at the pipes and other components are negligible.

To be solved in the class

In reality, the amount of heat rejected in the river will be lower because
a part of heat will be lost to the surroundings air from working fluid as it
passes through the pipes and other components.
Class exercise: Carnot Heat Engine
A Carnot heat engine
receive 500 kJ of
heat per cycle form a
high temperature
source of 652C and
reject a low
temperature sink at
30C as described in
given below Figure.
Heat Engine: Refrigeration cycle
• In a refrigeration process, a temperature lower than that
of the surroundings has to be maintained.

 Heat is absorbed at a low

temperature and continuously
rejected to the surroundings
which is at a higher temperature.
 The refrigeration cycle can thus be
thought of as a mechanism to pump
heat from a lower temperature to a
higher temperature.
 Reverse of a heat engine.
When installed backwards, an air
conditioner functions as a heat
pump
 Heat Engines: Carnot cycle
 To find the hypothetical maximum efficiency of a heat engine we can consider a
cycle called the Carnot Cycle first proposed by Sadi Carnot.
 The Carnot cycle is based entirely on reversible processes, this is not achievable in
reality.

Steps:
1. From a to b: Reversible adiabatic process to
increase temperature from 𝑇𝑐 (cold reservoir) to
𝑇𝐻 (hot reservoir)
2. From b to c: Reversible isothermal process
while |𝑄𝐻 | is absorbed from the hot reservoir
3. From c to d: Reversible adiabatic process to
decrease temperature from 𝑇𝐻 (hot reservoir)
to 𝑇𝐶 (cold reservoir)
4. From d to a: Reversible isothermal process
with rejection of heat |𝑄𝐶 | to the cold reservoir

Draw PV diagram for reversed Carnot cycle?

Explain. Fig. PV diagram showing Carnot
cycle for an ideal gas
The Carnot Principles
 The 2nd law of thermodynamics puts limits on the operation of cyclic
device as expressed by the Kelvin-Planck & Clausius statements.
 Considering heat engines operating between two fixed temperature
reservoir at TH  TC (TL). Two conclusions about the thermal efficiency of
reversible & irreversible heat engines known as Carnot Principles:

(a) The efficiency of an irreversible heat

engine is always less than the efficiency
of a reversible one operating between the
same two reservoirs.
th  th, Carnot

(b) The efficiencies of all reversible heat

engines operating between same two
constant temperature heat reservoir
have the same efficiency.
The Carnot Principles
• Carnot’s Theorem
• For two given heat reservoirs, no engine can have a thermal
efficiency higher than that of a Carnot engine.
• Corollaries to Carnot’s Theorem:
• The thermal efficiency of a Carnot engine depends only on
the temperature levels and not upon the working substance
of the engine.
• Let the Carnot engine C absorb heat |𝑄𝐻 | from the hot
reservoir, produce work |𝑊|, and discard heat 𝑄𝐻 − |𝑊| to
the cold reservoir. Engine E absorbs heat |𝑄𝐻′ | from the hot
reservoir, produces the same work 𝑊 and discards heat
𝑄𝐻′ − 𝑊 .
• If engine E has the greater efficiency
|𝑊| |𝑊|
′ > and 𝑄𝐻 > |𝑄𝐻′ |
|𝑄𝐻 | |𝑄𝐻 |
Heat Engines: Carnot cycle

• For the engine/refrigerator combination, the net heat extracted from

the cold reservoir is:
𝑄𝐻 − 𝑊 − 𝑄𝐻′ − 𝑊 = 𝑄𝐻 − |𝑄𝐻′ |
• The heat delivered to the hot reservoir is also 𝑄𝐻 − |𝑄𝐻′ |.
• The result is the transfer of heat
from temperature 𝑇𝑐 to a higher
temperature 𝑇𝐻 .
• According to statement 2 of the
second law of thermodynamics: No
Refrigerator process is possible which consists
(Reversed solely in the transfer of heat from
Carnot Engine) one temperature level to a higher
Engine one.
• Thus engine E cannot have a higher
thermal efficiency than Carnot
engine C. Carnot Theorem is proven.
For two given heat reservoirs, no engine
can have a thermal efficiency higher
than that of a Carnot engine.
Thermodynamic Temperature Scale
It can be shown that the thermal efficiency and the ratio of the heat source and
heat sink are functions of temperature:
𝑄𝐻 𝜓(𝑇𝐻 )
𝜂 = 𝜙 𝜃𝐻 , 𝜃𝐶 ; =
𝑄𝐶 𝜓(𝑇𝐶 )

Fig. Carnot engines 1 & 2 constitute a third Carnot engine

Ideal gas Temperature Scale: Carnot’s Equations

• 𝑎 → 𝑏 Adiabatic compression, 𝑇𝐶 to 𝑇𝐻
• 𝑏→𝑐 Isothermal expansion, absorbs
heat |𝑄𝐻 |
• 𝑐 → 𝑑 Adiabatic expansion, 𝑇𝐻 to 𝑇𝐶
• 𝑑 → 𝑎 Isothermal compression, releases
heat |𝑄𝐶 |

Fig. PV diagram showing Carnot

cycle for an ideal gas
Ideal gas Temperature Scale: Carnot’s Equations (Cont’d)

• For the isothermal processes (𝑏 → 𝑐 and 𝑑 → 𝑎):

𝑉𝐶 𝑉𝑑
𝑄𝐻 = 𝑅 𝑇𝐻 ln ; 𝑄𝐶 = 𝑅 𝑇𝐶 ln
𝑉𝑏 𝑉𝑎
|𝑄𝐻 | 𝑇𝐻 ln(𝑉𝐶 𝑉𝑏 )
= − (5.6)
|𝑄𝐶 | 𝑇𝐶 ln(𝑉𝑑 𝑉𝑎 )

• For the adiabatic processes (𝑎 → 𝑏 and 𝑐 → 𝑑):

𝑑𝑉
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑇 =0 − (3.22)
𝑉
𝑇𝐻 𝑇𝐻
𝐶𝑉 𝑑𝑇 𝑉𝑎 𝐶𝑉 𝑑𝑇 𝑉𝑑
= ln and = ln
𝑇𝐶 𝑅 𝑇 𝑉𝑏 𝑇𝐶 𝑅 𝑇 𝑉𝑐
𝑉𝑎 𝑉𝑑 𝑉𝑐 𝑉𝑑
→ ln = ln or ln = ln
𝑉𝑏 𝑉𝑐 𝑉𝑏 𝑉𝑎
|𝑄𝐻 | 𝑇𝐻 |𝑊| 𝑇𝐶
→ = → η≡ =1− − (5.8)
|𝑄𝐶 | 𝑇𝐶 |𝑄𝐻 | 𝑇𝐻
Class exercise: 3
A central power plant, rated at 800 000 kW, generates steam at 585 K and
discards heat to a river at 295 K. If the thermal efficiency of the plant is 70%
of the maximum possible value, how much heat is discarded to the river at
rated power?
Formulae:
|𝑊| 𝑇𝐶
Solution 𝜂= =1−
|𝑄𝐻 | 𝑇𝐻
Let 𝑇𝐻 = steam-generation temperature (585 K) 𝑊 = 𝑄𝐻 − |𝑄𝐶 |
𝑇𝐶 = river temperature (295 K)
The maximum possible thermal efficiency,
Derivation:
295 |𝑊|
𝜂𝑚𝑎𝑥 = 1 − = 0.4957 𝜂=
585 𝑊 + |𝑄𝐶 |
𝜂𝑎𝑐𝑡𝑢𝑎𝑙 = 0.7 0.4957 = 0.3470 𝑊
𝑊 + 𝑄𝐶 =
𝜂
Heat discarded to the river, 𝑊
𝑄𝐶 = − 𝑊
1−𝜂 1 − 0.3470 𝜂
|𝑄𝐶 | = 𝑊 = (800000) 1−𝜂
𝜂 0.3470 = 𝑊
𝜂
= 1505 500 kW
Self Assessment Exercise

1. A particular power plant operates with a heat source at 350 °C and

a heat sink reservoir at 30 °C. It has a thermal efficiency equal to
55% of the Carnot-engine thermal efficiency for the same temperatures.

a) What is the thermal efficiency of the plant?

b) To what temperature must the heat source reservoir be raised to increase
the thermal efficiency of the plant to 35%? Again, η is 55% of the Carnot-
engine value?

2. Briefly define the four processes by drawing

on P-V diagram that make up a Carnot cycle
Next class class contents

 Introduction of entropy
 Calculate Entropy for an ideal gas
 Understand the third law of thermodynamics
 Check List

 Introduce the second law of thermodynamics.

 Identify valid processes as those that satisfy both the first
and second laws of thermodynamics.
 Describe the Kelvin–Planck and Clausius statements of the
second law of thermodynamics.
 Discuss thermal energy reservoirs, reversible and
irreversible processes, and heat engines.
 Describe the Carnot cycle.
 Examine the Carnot principles and idealized Carnot heat
engines,
 Determine the expressions for the thermal efficiencies for
reversible heat engines .
Announcements for Make up Classes

Replacement class 1
Day/Date : Friday/18th July 2014
Venue : Pocket C6
Time : 03:00 pm – 05:00 pm

Replacement class 2
Day/Date : Friday/25th July 2014
Venue : Pocket C6
Time : 03:00 pm – 05:00 pm
Important Announcement:
 Quiz 2 will be held on July 23 (Wednesday)
Syllabus : Chapter 4 & 5

 Assignment 2 submission End date: 06-08-2014

 Assignment 3 submission End date: 20-08-2014

 Test 2 : 13th week (Chapter 4-7)